In situ immobilization of cadmium in soil by stabilized biochar-supported iron phosphate nanoparticles

The potential for nanoscale phosphate amendments to remediate heavy metal contamination has been widely investigated, but the strong tendency of nanoparticles to form aggregates limits the application of this technique in soil. This study synthesized a composite of biochar-supported iron phosphate nanoparticle (BC@Fe₃(PO₄)₂) stabilized by a sodium carboxymethyl cellulose to improve the stability and mobility of the amendment in soil. The sedimentation test and column test demonstrated that BC@Fe₃(PO₄)₂ exhibited better stability and mobility than iron phosphate nanoparticles. After 28 days of simulated in situ remediation, the immobilization efficiency of Cd was 60.2 %, and the physiological-based extraction test bioaccessibility was reduced by 53.9 %. The results of sequential extraction procedures indicated that the transformation from exchangeable (EX) Cd to organic matter (OM) and residue (RS) was responsible for the decrease in Cd leachability in soil. Accordingly, the pot test indicated that Cd uptake by cabbage mustard was suppressed by 86.8 %. Compared to tests using iron phosphate nanoparticles, the addition of BC@Fe₃(PO₄)₂ to soil could reduce the Fe uptake of cabbage mustard. Overall, this study revealed that BC@Fe₃(PO₄)₂ could provide effective in situ remediation of Cd in soil.     

In situ fixation of metals in soils using bauxite residue: chemical assessment

Contamination of soils with heavy metals and metalloids is a widespread problem all over the world. Low cost, non-invasive, in situ technologies are required for remediation processes. We investigated the efficiency of a bauxite residue (red mud) to fix heavy metals in two soils, one contaminated by industrial activities (French soil), and one by sewage sludge applications (UK soil). This Fe-oxide rich material was compared with lime, or beringite, a modified aluminosilicate that has been used for in situ fixation processes. Four different crop species were successively grown in pots. Metal concentrations in the soil pore waters were analyzed during the growing cycles. At the end of the experiment fluxes of heavy metals were measured using a diffusive gradient in thin film technique (DGT). Furthermore, a sequential extraction procedure (SEP) and an acidification test were performed to investigate the mechanisms of metal fixation by different soil amendments. In both soils, the concentrations of metals in the soil pore water and metal fluxes were greatly decreased by the amendments. An application of 2% red mud performed as well as beringite applied at 5%. Increasing soil pH was a common mechanism of action for all the amendments. However, the red mud amendment shifted metals from the exchangeable to the Fe-oxide fraction, and decreased acid extractability of metals. The results suggest that specific chemisorption, and possibly metal diffusion into oxide particles could also be the mechanisms responsible for the fixation of metals by red mud.     

In situ fixation of metals in soils using bauxite residue: biological effects

Soils polluted with heavy metals can cause phytotoxicity and exhibit impared microbial activities. In this paper we evaluate the responses of different biological endpoints to in situ remediation processes. Three soil amendments (red mud, beringite and lime) were applied to two soils polluted by heavy metals. Oilseed rape, wheat, pea and lettuce were grown successively in pots on the untreated and amended soils and their yield and metal uptake were determined. A suite of microbial tests (lux-marked biosensors, Biolog and soil microbial biomass) were performed to determine the effect of the soil amendments on the functionality and size of the soil microbial community. In both soils all three amendments reduced phytotoxicity of heavy metals, enhanced plant yields and decreased the metal concentrations in plants. The red mud treatment also increased soil microbial biomass significantly. The microbial biosensors responded positively to the remediation treatments in the industrially-contaminated soil used in the experiment. Red mud applied at 2% of soil weight was as effective as beringite applied at 5%. The results also showed that since the biological systems tested respond differently to the alleviation of metal toxicity, a suite of biological assays should be used to assess soil remediation processes.     

Regeneration of spent TiO2 nanoparticles for Pb (II), Cu (II), and Zn (II) removal

Spent sorbents in water treatment processes have potential risks to the environment if released without proper treatment. The aim of this work was to investigate the potential regeneration of commercially prepared nano-TiO₂ (anatase) for the removal of Pb (II), Cu (II), and Zn (II) by pH 2 and ethylenediaminetetraacetic acid (EDTA) solutions. The percent of metal adsorption/desorption decreased with the increasing number of regeneration cycles, and the extent of decrease varied for each metal. Competitive effects were observed for the adsorption/desorption of different metals when the nano-TiO₂ was regenerated by EDTA solutions. Nano-TiO₂ was able to treat simulated metal polluted water with greater than 94 % adsorption and greater than 92 % desorption after four cycles of regeneration using pH 2 solution. These results demonstrated that nano-TiO₂ can be regenerated and reused using pH 2 solution compared to an EDTA solution for aquatic metal removal, which makes nanosorbents promising and economically and environmentally more attractive in the application of water purification.     

In situ remediation of soils contaminated with toxic metal ions using microwave energy

Following onto our work on the in situ remediation of soils contaminated with PAH's, PCB's and other polychlorinated organic compounds using microwave energy, we now report a preliminary investigation on the in situ remediation of soils contaminated with toxic metal ions: Cd(II), Mn(II), Th(IV), Cr(III) and mainly Cr(VI). The soil is partially vitrified in the process, and extraction with hot (70 degrees C) 35% nitric acid for 4.5 h leads to the recovery of very small amounts of the metals which had been spiked into the clean soil: Cd, Mn, and Cr(III) are completely immobilized (unextractable), Th is mostly unextractable, and Cr(VI) partially extractable at very high levels of spiking, but almost completely unextractable using the US EPA Toxicity Characteristic Leaching Procedure. This suggests that contaminated soils which are not going to be used for agricultural purposes can be remediated safely to preset depths without fear of the toxic metal ions leaching out for a long time.     

植物混种原位修复多环芳烃污染农田土壤

通过比较实验前后土壤微生物主要类群数量、PAHs降解菌数量、土壤PAHs含量和植物不同部位PAHs含量变化,评价植物单种和混种野外原位修复多环芳烃(PAHs)污染农田土壤的效果。结果显示,150 d天生长期内,黑麦草/小麦混种及黑麦草/蚕豆混种修复效果最好,对土壤PAHs总量的降解率分别达到了59.4%和64.8%。同时,这2个混种处理土壤细菌、真菌和PAHs降解菌数量分别显著高于相应的小麦、蚕豆和黑麦草单种处理。植物不同部位PAHs含量高低次序为根部>茎叶≈籽粒。混种模式下,蚕豆和小麦不同部位PAHs含量比单种模式的不同程度降低,特别是籽粒部。植物混种模式不仅显著提高了土壤PAHs的降解率,还降低了农作物体内PAHs含量,实现了边生产边修复,在污染农田土壤修复领域有着广阔的应用前景。     

Cu(II) removal from aqueous solution using Dogantepe (Amasya) zeolites

This paper investigates the effects of zeolite particle size, zeolite/ solution ratio and stirring time on the performance of zeolites from Dogantepe in removing Cu(II) from aqueous solution to establish optimum operating conditions. The results indicated that the size of the zeolite samples, the concentration of Cu(II) and the zeolite/solution ratio affected the removal efficiencies, whilst the stirring time was found to have no significant effect on the removal efficiencies. The equivalent numbers of sodium, magnesium, calcium and potassium ions passed into the Cu(II) solution were found to be 1.196, 0.208, 0.117 and 0.009 meq/l, respectively, and the passing percentages of these ions were calculated to be 11.27, 2.45, 1.57 and 0.37%, respectively. The removal mechanism of Cu(II) with zeolite samples was mainly ion exchange with a fraction of approximately 65%. The maximum exchange capacities obtained by using Dogantepe zeolites, Yavu zeolites, and synthetic resin were found to be 9.2, 7.0 and 72.7 mg/g, respectively. However, in relatively low concentrations of Cu(II), the differences in the removal efficiencies or exchange capacities obtained for above different three materials were significantly decreased.     

Effect of biochars on adsorption of Cu(II), Pb(II) and Cd(II) by three variable charge soils from southern China

The purpose of this study is to compare the relative contribution of different mechanisms to the enhanced adsorption of Cu(II), Pb(II) and Cd(II) by variable charge soils due to incorporation of biochars derived from crop straws. The biochars were prepared from the straws of canola and peanut using an oxygen-limited pyrolysis method at 350 °C. The effect of biochars on adsorption and desorption of Cu(II), Pb(II) and Cd(II) by and from three variable charge soils from southern China was investigated with batch experiments. Based on the desorption of pre-adsorbed heavy metals, the electrostatic and non-electrostatic adsorptions were separated. EDTA was used to replace the heavy metals complexed with biochars and to evaluate the complexing ability of the biochars with the metals. The incorporation of biochars increased the adsorption of Cu(II), Pb(II) and Cd(II) by the soil; peanut straw char induced a greater increase in the adsorption of the three metals. The increased percentage of Cd(II) adsorption induced by biochars was much greater than that for the adsorption of Cu(II) and Pb(II). Cu(II) adsorption on three variable charge soils was enhanced by the two biochars mainly through a non-electrostatic mechanism, while both electrostatic and non-electrostatic mechanisms contributed to the enhanced adsorption of Pb(II) and Cd(II) due to the biochars. Peanut straw char had a greater specific adsorption capacity than canola straw char and thus induced more non-electrostatic adsorption of Cu(II), Pb(II) and Cd(II) by the soils than did the canola straw char. The complexing ability of the biochars with Cu(II) and Pb(II) was much stronger than that with Cd(II) and thus induced more specific adsorption of Cu(II) and Pb(II) by the soils than that of Cd(II). Biochars increased heavy metal adsorption by the variable charge soils through electrostatic and non-electrostatic mechanisms, and the relative contribution of the two mechanisms varied with metals and biochars.     

In situ transformations of fine lead oxide particles in different soils

We present a field application of a new in situ technique to analyze phase transformations of fine lead oxide particles (50-100mum) in different soils directly in the field over 18 months. After the first month of exposure to a calcareous sand we found newly precipitated secondary mineral phases on the lead oxide. The samples exposed to two loamy soils (Dystric Cambisol and Luvisol) showed only very few traces of new phases. We identified the new phases as mainly lead-hydroxy carbonates (hydrocerussite). Whereas the results confirm the transformation of lead phases to lead carbonates in calcareous soil, they also show that an easily soluble phase such as PbO may persist in soils virtually unweathered for more than one year. The formation of a weathering crust is therefore not necessarily needed for preservation of easily soluble phases. The use of experimental in situ methods is thus giving new information on contaminant mineral behavior under field conditions.     

Representative measurement of two-dimensional reactive phosphate distributions and co-distributed iron(II) and sulfide in seagrass sediment porewaters

The high degree of heterogeneity within sediments can make interpreting one-dimensional measurements difficult. The recent development and use of in situ techniques that measure two-dimensional distributions of porewater solutes have facilitated investigation of the role of spatial heterogeneity in sediment biogeochemistry. A colourimetric diffusive equilibration in thin films method has been developed that allows two-dimensional, high-resolution measurement of reactive phosphate in sediment porewaters. A method detection limit of 0.22 μM, an effective upper limit of ∼1000 μM and relative standard deviations typically below 5% were achieved. This method was evaluated by deployment in seagrass (Zostera capricorni) colonised sediments, as part of combined probes with similar colourimetric methods for sulfide and iron(II). The two-dimensional, high resolution distributions obtained provide a highly representative measurement of the co-distributions of porewater solutes, allowing heterogeneous features and biogeochemical processes to be observed and interpreted. Microniches of high phosphate concentration >100 μM were observed throughout the distributions and were interpreted to be due to localised zones of rapid organic matter mineralisation, possibly using electron acceptors other than iron(III) oxyhydroxides (e.g. aerobic respiration) as often they did not correspond with microniches of higher Fe(II) concentration.     

Impacts of horseradish peroxidase immobilization onto functionalized superparamagnetic iron oxide nanoparticles as a biocatalyst for dye degradation

Environmental Science and Pollution Research - To enhance the dye removal efficiency by natural enzyme, horseradish peroxidase (HRP) was immobilized onto amine-functionalized superparamagnetic iron...     

Removal of Cu(II) from aqueous solution in a fluidized-bed reactor

In this study, a fluidized-bed reactor (FBR) was employed to treat copper-containing wastewater by mean of copper precipitation on the surface of sand grains. The conditions for optimum copper removal efficiency were also investigated. This technology was controlled so as to keep supersaturation low to induce the nucleated precipitation of copper coating on the sand surface in an FBR. The effects of relevant parameters, such as the pH value, the molar ratio of [C(T)] to [Cu(2+)], hydraulic loading and the types of chemical reagents used, were examined. The experimental results indicated that 96% copper removal efficiency could be achieved when the influent copper concentration was 10mg l(-1). The optimum chemical reagent was Na(2)CO(3); the molar ratio of [C(T)]/[Cu(2+)] was 2, and the optimal hydraulic loading was not be more than 25m h(-1). In addition, preventing homogeneous nucleation in the FBR was an important operation parameter. Homogeneous nucleation and molecular growth would lead to undesirable microparticle formation in the effluent. A good mixture of carbonate and copper in the presence of sand grains could reduce the level of homogeneous nucleation in the bottom of the reactor. Energy dispersive analysis (EDS) of X-rays provided insight into the copper coating on the sand surface, and element analysis indicated the weight percentages of CuCO(3) and Cu(OH)(2) in precipitate.     

Zero-valent iron nanoparticles in treatment of acid mine water from in situ uranium leaching

Acid mine water from in situ chemical leaching of uranium (Straz pod Ralskem, Czech Republic) was treated in laboratory scale experiments by zero-valent iron nanoparticles (nZVI). For the first time, nZVI were applied for the treatment of the real acid water system containing the miscellaneous mixture of pollutants, where the various removal mechanisms occur simultaneously. Toxicity of the treated saline acid water is caused by major contaminants represented by aluminum and sulphates in a high concentration, as well as by microcontaminants like As, Be, Cd, Cr, Cu, Ni, U, V, and Zn. Laboratory batch experiments proved a significant decrease in concentrations of all the monitored pollutants due to an increase in pH and a decrease in oxidation-reduction potential related to an application of nZVI. The assumed mechanisms of contaminants removal include precipitation of cations in a lower oxidation state, precipitation caused by a simple pH increase and co-precipitation with the formed iron oxyhydroxides. The possibility to control the reaction kinetics through the nature of the surface stabilizing shell (polymer vs. FeO nanolayer) is discussed as an important practical aspect.     

Precipitation of Zn(II), Cu(II) and Pb(II) at bench-scale using biogenic hydrogen sulfide from the utilization of volatile fatty acids

Biological production of hydrogen sulfide (H(2)S) using sulfate-reducing bacteria (SRB) has important potential within environmental biotechnology. The aim of this work was to study the possibility of using SRB for the treatment of an acid mine drainage (AMD) at bench-scale. This process involved three stages: the optimization of H(2)S production through the utilization of total volatile fatty acids (TVFAs) by SRB, the establishment of a biofilm reactor for sulfide production, and the precipitation of metals by using the biologically produced H(2)S. The substrates used for TVFAs production consisted of papaya, apple and banana. The H(2)S produced from the degradation of TVFAs was utilized for the precipitation of a metal-contaminated effluent collected from Bolivar mine (Oruro, Bolivia). The maximum concentration of H(2)S obtained was approximately 16mM. Removal efficiencies of ca. 100% for copper, above 94% for zinc, and above 92% for lead were achieved.     

Simultaneous extraction of Cr(VI) and Cu(II) from humic acid with new synthesized EDTA derivatives

Soil washing is one of the few permanent treatment alternatives for removing metal contaminants. Ethylenediaminetetraacetic acid and its salts (EDTA) is very effective at removing cationic metals and has been utilized globally. However it is ineffective for anionic metal contaminants or metals bound to soil organic matter. The simultaneous removal of cationic and anionic metal contaminants by soil washing is difficult due to differences in their properties. The present study evaluated the potential of a washing process using two synthesized EDTA-derivatives, C₆HEDTA (2,2′-((2-((carboxymethyl)(2-(hexanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid) and C₁₂HEDTA (2,2′-((2-((carboxymethyl) (2-(dodecanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid), which consist of a hydrophilic polycarboxylic moiety and a hydrophobic moiety with a monoalkyl ester group. A series of equilibrium batch experiments at room temperature were conducted to investigate the efficacy of C₆HEDTA and C₁₂HEDTA as extractants for both oxyanion Cr(VI) and cationic Cu(II). Results showed that either C₆HEDTA or C₁₂HEDTA can extract both Cr(VI) and Cu(II) from humic acid simultaneously. However, C₆HEDTA was less effective for Cr(VI) probably because it has no surface activities to increase solubility of humic acid, like C₁₂HEDTA. Extraction of Cr(VI) was mainly attributed to the decreased surface tension and enhanced solubility of organic matter. Extraction of Cu(II) was attributed to both the Cu(II) chelation and enhanced solubility of humic acid. It was demonstrated that the hydrophilic polycarboxylic moiety of C₁₂HEDTA chelates cations while the monoalkyl ester group produces surface active properties that enhance the solubility of humic acid.     

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.     

Removal of Pb(II) and Cd(II) ions from water by Fe and Ag nanoparticles prepared using electro-exploding wire technique

Purpose

This work aimed at investigating the adsorption of lead and cadmium onto Fe and Ag nanoparticles for use as a water contaminant removal agent as a function of particle type, sorbent concentration, and contact time.

Methods

Fe and Ag spherical nanoparticles were prepared in water by the lab-made electro-exploding wire (EEW) system and were investigated for their structure properties. Adsorption experiments were carried out at room temperature and pH 8.3 water solutions.

Results

The removal/adsorption of both Pb(II) and Cd(II) ions was found to be dependent on adsorbent dosage and contact time. Pb(II) adsorption onto Fe and Ag nanoparticles showed more or less similar efficiency and behavior. The kinetic data for the adsorption process obeyed pseudo second-order rate equations. The calculated equilibrium adsorption capacities (q _e) were 813 and 800 mg/g for Pb sorption onto Fe and Ag nanoparticles, respectively. Cd(II) ion adsorption onto Fe nanoparticles obeyed pseudo second-order rate equations with q _e equal to 242 mg/g, while their adsorption onto Ag nanoparticles obeyed pseudo first-order rate equations with q _e of 794 mg/g. The calculated q _es are in quite agreement with the experimental values. The removal/uptake mechanisms of metal ions involved interaction between the metal ion and the oxide/hydroxyl layer around the spherical metallic core of the nanoparticle in water medium.

Conclusion

Fe and Ag nanoparticles prepared using the EEW technique exhibited high potentials for the removal of metal ions from water with very high adsorption capacities, suggesting that the EEW technique can be enlarged to generate nanoparticles with large quantities for field or site water purification.     

Cu(II) removal using green adsorbents: kinetic modeling and plant scale-up design

Cu(II) adsorption in continuous column using green adsorbents like peanut and almond shell was investigated. Fourier transform infrared (FTIR) spectroscopy, Brunaer-Emmett-Teller (BET) analysis, scanning electron microscopy (SEM), and Point of Zero charge (pH_pzc) determination have been used for characterization of the adsorbents. Experiments were conducted at various operating conditions to calculate the adsorption capacity of the adsorbents. Adsorption studies signify that both the adsorbents have good adsorptive capacity for Cu(II) ion. Equilibrium of adsorption was described using Langmuir isotherm and the highest q_max value for both the adsorbent were obtained at an operating condition of 20 ml/min flow rate, 15 mg/L influent Cu(II) concentration, and 7 cm bed depth. Regeneration of both the adsorbents suggests that these adsorbents can be used several times for Cu(II) removal. Seven different kinetic models were tested among which the modified dose response model was fitted well for peanut shell and the Thomas model was fitted well for almond shell. These fitted models were further used for scale-up design. Regeneration studies show that peanut shell and almond shell are useful up to the fifth adsorption cycle. Application of these adsorbents with industrial effluent was also reported. This study reveals that peanut and almond shells can be used for Cu(II) removal for industrial wastewater.

     

Modeling interactions of Hg(II) and bauxitic soils

The adsorptive interactions of Hg(II) with gibbsite-rich soils (hereafter SOIL-g) were modeled by 1-pK surface complexation theory using charge distribution multi-site ion competition model (CD MUSIC) incorporating basic Stern layer model (BSM) to account for electrostatic effects. The model calibrations were performed for the experimental data of synthetic gibbsite-Hg(II) adsorption. When [NaNO(3)] > or = 0.01M, the Hg(II) adsorption density values, of gibbsite, Gamma(Hg(II)), showed a negligible variation with ionic strength. However, Gamma(Hg(II)) values show a marked variation with the [Cl(-)]. When [Cl(-)] > or = 0.01M, the Gamma(Hg(II)) values showed a significant reduction with the pH. The Hg(II) adsorption behavior in NaNO(3) was modeled assuming homogeneous solid surface. The introduction of high affinity sites, i.e., >Al(s)OH at a low concentration (typically about 0.045 sites nm(-2)) is required to model Hg(II) adsorption in NaCl. According to IR spectroscopic data, the bauxitic soil (SOIL-g) is characterized by gibbsite and bayerite. These mineral phases were not treated discretely in modeling of Hg(II) and soil interactions. The CD MUSIC/BSM model combination can be used to model Hg(II) adsorption on bauxitic soil. The role of organic matter seems to play a role on Hg(II) binding when pH>8. The Hg(II) adsorption in the presence of excess Cl(-) ions required the selection of high affinity sites in modeling.